CA1204792A - Refractory gun mix - Google Patents
Refractory gun mixInfo
- Publication number
- CA1204792A CA1204792A CA000434475A CA434475A CA1204792A CA 1204792 A CA1204792 A CA 1204792A CA 000434475 A CA000434475 A CA 000434475A CA 434475 A CA434475 A CA 434475A CA 1204792 A CA1204792 A CA 1204792A
- Authority
- CA
- Canada
- Prior art keywords
- aggregate
- cao
- lime
- mgo
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 28
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 28
- 239000004571 lime Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 18
- 235000012245 magnesium oxide Nutrition 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 5
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 34
- 239000011822 basic refractory Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000002893 slag Substances 0.000 abstract description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 5
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- 239000011819 refractory material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960003563 calcium carbonate Drugs 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 241000669761 Aggregata Species 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000243251 Hydra Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/057—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on calcium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
- C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
- C04B2235/3454—Calcium silicates, e.g. wollastonite
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Products (AREA)
Abstract
ABSTRACT
A low cost stabilized lime aggregate, preferably with dicalcium silicate as a major constituent, is obtained from slags of specified composition, and finds use in refractory gun mixes. Briefly, the slags which are suitable for this application contain at least 75% total CaO + Fe2O3 + SiO2 + MgO, have a CaO:SiO2 weight ratio of at least 1.8, less that 7% total calcium carbonate (CaCO3), calcium hydroxide (Ca(OH)2), and CaO, and prefer-ably contain at least 20% CaO.
A low cost stabilized lime aggregate, preferably with dicalcium silicate as a major constituent, is obtained from slags of specified composition, and finds use in refractory gun mixes. Briefly, the slags which are suitable for this application contain at least 75% total CaO + Fe2O3 + SiO2 + MgO, have a CaO:SiO2 weight ratio of at least 1.8, less that 7% total calcium carbonate (CaCO3), calcium hydroxide (Ca(OH)2), and CaO, and prefer-ably contain at least 20% CaO.
Description
~ 4 ~ ~ Case 6407 REFR~CTORY GUN MIX
Background of the Invention This inven~ion pertains to refractory gun mixes, particularly such mixes containing a significant por~ion of stabili2ed lime aggregate.
Both the refractories producer and the reractorles user have sought for many years to reduce ~heir costs, for example by searching for lower cos~ refractory aggregates.
One very abundant, and ~herefore low cost, material of great refractoriness is lime (CaO)~ However, 10 this material shows such a marked tendency to hydra~e in the presence of any moisture, and also to form calcium carbonate (CaCO3) in the presenc~ of carbon dioxide (CO2), that i~ is essentially useless as a refractory material, except in the most specialized circumstances.
Another very abundant, low cost source of refractory aggregate is dolomite, a roughly equimolar mixture of magnesi~m and calcium carbonates. This material is widely used as a refractory raw material7 pDrticularl~ in Europe, but also to a significant cxtent in the United S~ates. How-2Q ever, it too suffers from the tendency of the lime contained in it to hydrate, and special precautions must be ~aken in using dolomite refractories to deal with this hydration tendency.
The present invention is directed to the use 25 of another relatively low cost refractory material, the ma-terial referred to herein as "stabilized 7ime aggrega~e".
While this material can be ob~ained from various sources, because o~ their great abundance and relative low cos~, slags, for example slags from steelmaking processes, have 30 proved to be a good source of this stabilized lime aggregate.
The use of slags in refractory materials has long been known; for example 9 US 710,916 sugges~s the use of slag in a ramming mix for lining converters or furnacesO
The use of slag is also suggested in US 3,798,043, US 4,222,786 and in British Application 2,058~041. However, the slag~ suggested for use in these patents differ signi~i-can~ly from the materials used in ~he practice of the present invention.
Summar~ o the Invention It has now been ound according to this invention tha~ a gun mlx of good performance and relatively low cost i5 ob~ained when it corlsists essentially of rom 5 to 95%
of a stabilized lime aggregate, ~aid aggregate containing at least 75% total CaO ~ Fe203 + SiO2 ~ MgO, ~he remainder being other refractory oxides~ the CaO:SiO2 weight ratio being at least 1.8, whereby dicalcium silicate is 8 ma~or crystalline phase in the aggregate, said aggregate having less than 7% free~lime, from 1 to 10% of a basic inorganic 15 bond, and from ~ to 5% pla~ticizer, the balance of the composition being basic refractory aggregate, all percen~ages being by weight based on the total weight of the composition.
Detailed Descri~tion The stabili~ed lime aggrega~e used in this 20 invention may be obtained frsm any suitable source, providing the material has the specifie~ chemical composition; bu~ for reasons of economy it is preferred tha~ ~he source be a slag material. Such materials are produced in various s~eelmak-ing processes and are regarded as essentially waste products from such processes. Accordingly, they are readily available at re~atively low cost.
The important characteristic of ~he st~bilized lime aggregate of this invention is its chemical composi-tion: it will contain at least 75% CaO + Fe203 ~ SiO
3~ MgO and the weight ratio o~ CaO to SiO2 will be at least 1.8. Tho5e skilled in thc art will recognize tha~ this weight ratio of lime to silica indicates that lime and silica will combin~ to form dicalcium silicate. of course, in the presence of significant amounts of Fe203, other crystalline compounds of iron and/or lime and/or silica will form. It is also essential that the aggregate have a minimum amount, less than 7%, and preferably less than 5%, of lime in a form1 for example either CaO, or calcium car-bonate or calcium hydroxide, which is not combined with ano~her refractory oxide. Such uncombined lime is herein referred to as "ree llme". While the chemical constituents of ~he stabilized lim~ aggregate will largely be present in the form of crystalline compounds, slags are generally regarded as glassy materials (since they exist in he molten state in the steelmaking processes, and are rapidly cooled when discharged from such processes, they will often contain a significant amount of glassy material). However, a slag containing the specifled overall chemical composition will be sui~able for use in t.his invention.
In addition to the s~abilized lime aggregate 3 gun mix composi~ions according to this invention may also contain other refrac~ory aggrega~es, pre~erably basic aggregates such as periclase and/or chrome ore. Most preferably, gun mixes according to the present invention, if they contain any ag-grega~e in addition to the stabilized lime aggregate, con-tain a periclase containing at least 80% MgO.
The aggregate will be sized according to good practice, as is well-kn~wn to those skilled in the ar~, to achieve good flow through the gunning apparatus and good adherence and density when placed~ for example on a furnace wall.
Also, the gun mixes of ~he present inven~ion will contain a suitable bond, any of various bonds well-known for this purpose being suitable. Specific examples of such bonds are given in the examples which follow.
In addition, as is conventional in gun mixes, the compositions will contain a plasticizer, either an organic plasticizer (in which case ~he amount used will be rela-tively low, for example from 0.05 to 1%) or a mineral plasticizer such as ben~onite (in which case a rela~ively la~ger amount will b~ used, for example from 1 to 5%~
These varlous ingredients will be admixed by the rPractories manufacturer and shipped to the customer, for e~ample in bags containing 25 or 50 kg (50 or 100 pound sacks), or even larger containers. The user will place the composition in a re~ractory gun or s-Lmilar apparatus and use it to repair or main~ain a furnace lining by gunning onto the sur~ace of the lining9 either when it is still hot, or after it has cooled down, all as is well-known in this0 art.
amples Table I show~ the compositions o various gun mi~es within the scope of this invention~ together with certain compariso~ composi~ions. Specifically, Composition~
1 through 12 are within ~he scope o~ the present invention whereas Compositions 13, 14 and 15 are comparison eæamples.
The amounts shown are parts by weight. The chemical analyses o~ the various aggregates used are given in Table TI.
Stabilized lime aggregata A is an ope~ hearth slag, whereas B is a BOF (basic o~ygen furnac0) slag, a~d C
is an EAF (electric arc furnace) slag. Aggregates D, E and F, which are used in the comparison examples not wi~hin the scope of this invention, are, respectively, a so-called "nickel" slag, a blast furnace slag, and a desulfurization blast furnace slag. The term "desulfurization" reers to the poin~ in the iron making proce~s at which the slag is used.
Table I also indicates the types and amounts of the various bonding materials used with these gun mixes, all these bonds being generally well-known in the ar~ and the subject o United States patents. Specifically, the bond used in Compositions 1, 2 ~nd 7 is the subject of US 4,276,091; the bond used in Compositions 3, 4, 5, 6, 8, and 10 through 15 is ~he subject of US 4,244,744; and the bond used in Composition 9 is the subjec~ of US 49001,029.
~4~-o G~ O
C~ o C'~ ~ ~o .. ,,,, .
cr~ ~1 o C~l ~ oo U~ ,, ., o a~
oo o o ~
cr ~ o o U~ . . .
oo o o oo ¢ ~ ' ' ' ' ' ' ' ' -~ ~ ~ I~ o H C~ C`l O~ r-l u 1~1 C`l ~D
1~ oo C~ ~1 O
_I ~1 ~
r~ oo ~ ~o a I I
.,1 ~ ~ a~
~q ~ ~-rl $
~9 P a~
O
C~ 'tl $ U~ C~) J' ~ ~IIIII ~
O O
O~0 0 ¢ :q TABLE II
Aggregate A B C* D E F X Y
CaO 24.2 39.8 35 2.4 35.1 13.4 1.0 48.9 SiO2 1~.6 12~7 2~ 34.1 38.6 13.6 2-1 0.6 Fe2~3 44.4 25.5 20 48.5 1.1 63.1 0.6 11.0 MgQ 7.7 9.2 S 6.2 16.5 5.2 95.5 39.1
Background of the Invention This inven~ion pertains to refractory gun mixes, particularly such mixes containing a significant por~ion of stabili2ed lime aggregate.
Both the refractories producer and the reractorles user have sought for many years to reduce ~heir costs, for example by searching for lower cos~ refractory aggregates.
One very abundant, and ~herefore low cost, material of great refractoriness is lime (CaO)~ However, 10 this material shows such a marked tendency to hydra~e in the presence of any moisture, and also to form calcium carbonate (CaCO3) in the presenc~ of carbon dioxide (CO2), that i~ is essentially useless as a refractory material, except in the most specialized circumstances.
Another very abundant, low cost source of refractory aggregate is dolomite, a roughly equimolar mixture of magnesi~m and calcium carbonates. This material is widely used as a refractory raw material7 pDrticularl~ in Europe, but also to a significant cxtent in the United S~ates. How-2Q ever, it too suffers from the tendency of the lime contained in it to hydrate, and special precautions must be ~aken in using dolomite refractories to deal with this hydration tendency.
The present invention is directed to the use 25 of another relatively low cost refractory material, the ma-terial referred to herein as "stabilized 7ime aggrega~e".
While this material can be ob~ained from various sources, because o~ their great abundance and relative low cos~, slags, for example slags from steelmaking processes, have 30 proved to be a good source of this stabilized lime aggregate.
The use of slags in refractory materials has long been known; for example 9 US 710,916 sugges~s the use of slag in a ramming mix for lining converters or furnacesO
The use of slag is also suggested in US 3,798,043, US 4,222,786 and in British Application 2,058~041. However, the slag~ suggested for use in these patents differ signi~i-can~ly from the materials used in ~he practice of the present invention.
Summar~ o the Invention It has now been ound according to this invention tha~ a gun mlx of good performance and relatively low cost i5 ob~ained when it corlsists essentially of rom 5 to 95%
of a stabilized lime aggregate, ~aid aggregate containing at least 75% total CaO ~ Fe203 + SiO2 ~ MgO, ~he remainder being other refractory oxides~ the CaO:SiO2 weight ratio being at least 1.8, whereby dicalcium silicate is 8 ma~or crystalline phase in the aggregate, said aggregate having less than 7% free~lime, from 1 to 10% of a basic inorganic 15 bond, and from ~ to 5% pla~ticizer, the balance of the composition being basic refractory aggregate, all percen~ages being by weight based on the total weight of the composition.
Detailed Descri~tion The stabili~ed lime aggrega~e used in this 20 invention may be obtained frsm any suitable source, providing the material has the specifie~ chemical composition; bu~ for reasons of economy it is preferred tha~ ~he source be a slag material. Such materials are produced in various s~eelmak-ing processes and are regarded as essentially waste products from such processes. Accordingly, they are readily available at re~atively low cost.
The important characteristic of ~he st~bilized lime aggregate of this invention is its chemical composi-tion: it will contain at least 75% CaO + Fe203 ~ SiO
3~ MgO and the weight ratio o~ CaO to SiO2 will be at least 1.8. Tho5e skilled in thc art will recognize tha~ this weight ratio of lime to silica indicates that lime and silica will combin~ to form dicalcium silicate. of course, in the presence of significant amounts of Fe203, other crystalline compounds of iron and/or lime and/or silica will form. It is also essential that the aggregate have a minimum amount, less than 7%, and preferably less than 5%, of lime in a form1 for example either CaO, or calcium car-bonate or calcium hydroxide, which is not combined with ano~her refractory oxide. Such uncombined lime is herein referred to as "ree llme". While the chemical constituents of ~he stabilized lim~ aggregate will largely be present in the form of crystalline compounds, slags are generally regarded as glassy materials (since they exist in he molten state in the steelmaking processes, and are rapidly cooled when discharged from such processes, they will often contain a significant amount of glassy material). However, a slag containing the specifled overall chemical composition will be sui~able for use in t.his invention.
In addition to the s~abilized lime aggregate 3 gun mix composi~ions according to this invention may also contain other refrac~ory aggrega~es, pre~erably basic aggregates such as periclase and/or chrome ore. Most preferably, gun mixes according to the present invention, if they contain any ag-grega~e in addition to the stabilized lime aggregate, con-tain a periclase containing at least 80% MgO.
The aggregate will be sized according to good practice, as is well-kn~wn to those skilled in the ar~, to achieve good flow through the gunning apparatus and good adherence and density when placed~ for example on a furnace wall.
Also, the gun mixes of ~he present inven~ion will contain a suitable bond, any of various bonds well-known for this purpose being suitable. Specific examples of such bonds are given in the examples which follow.
In addition, as is conventional in gun mixes, the compositions will contain a plasticizer, either an organic plasticizer (in which case ~he amount used will be rela-tively low, for example from 0.05 to 1%) or a mineral plasticizer such as ben~onite (in which case a rela~ively la~ger amount will b~ used, for example from 1 to 5%~
These varlous ingredients will be admixed by the rPractories manufacturer and shipped to the customer, for e~ample in bags containing 25 or 50 kg (50 or 100 pound sacks), or even larger containers. The user will place the composition in a re~ractory gun or s-Lmilar apparatus and use it to repair or main~ain a furnace lining by gunning onto the sur~ace of the lining9 either when it is still hot, or after it has cooled down, all as is well-known in this0 art.
amples Table I show~ the compositions o various gun mi~es within the scope of this invention~ together with certain compariso~ composi~ions. Specifically, Composition~
1 through 12 are within ~he scope o~ the present invention whereas Compositions 13, 14 and 15 are comparison eæamples.
The amounts shown are parts by weight. The chemical analyses o~ the various aggregates used are given in Table TI.
Stabilized lime aggregata A is an ope~ hearth slag, whereas B is a BOF (basic o~ygen furnac0) slag, a~d C
is an EAF (electric arc furnace) slag. Aggregates D, E and F, which are used in the comparison examples not wi~hin the scope of this invention, are, respectively, a so-called "nickel" slag, a blast furnace slag, and a desulfurization blast furnace slag. The term "desulfurization" reers to the poin~ in the iron making proce~s at which the slag is used.
Table I also indicates the types and amounts of the various bonding materials used with these gun mixes, all these bonds being generally well-known in the ar~ and the subject o United States patents. Specifically, the bond used in Compositions 1, 2 ~nd 7 is the subject of US 4,276,091; the bond used in Compositions 3, 4, 5, 6, 8, and 10 through 15 is ~he subject of US 4,244,744; and the bond used in Composition 9 is the subjec~ of US 49001,029.
~4~-o G~ O
C~ o C'~ ~ ~o .. ,,,, .
cr~ ~1 o C~l ~ oo U~ ,, ., o a~
oo o o ~
cr ~ o o U~ . . .
oo o o oo ¢ ~ ' ' ' ' ' ' ' ' -~ ~ ~ I~ o H C~ C`l O~ r-l u 1~1 C`l ~D
1~ oo C~ ~1 O
_I ~1 ~
r~ oo ~ ~o a I I
.,1 ~ ~ a~
~q ~ ~-rl $
~9 P a~
O
C~ 'tl $ U~ C~) J' ~ ~IIIII ~
O O
O~0 0 ¢ :q TABLE II
Aggregate A B C* D E F X Y
CaO 24.2 39.8 35 2.4 35.1 13.4 1.0 48.9 SiO2 1~.6 12~7 2~ 34.1 38.6 13.6 2-1 0.6 Fe2~3 44.4 25.5 20 48.5 1.1 63.1 0.6 11.0 MgQ 7.7 9.2 S 6.2 16.5 5.2 95.5 39.1
2~ ~.8 1.2 12 6-0 6.8 3.1 0~4 0.3 MnO 5.2 4.6 120.05 0.5 0.9 Cr203 0.5 0.1 5 0.1 0.1 0.1 0.4 TiO2 0 9 0.8Ø50.2 0,4 0.3 - 0.1 P205 1.2 1.2 - 0.01 0.1 ~0.05 - -F 0.3 0.8 S 0.~ 0.1 - - _ _ _ _ ~2 ~ ~ - 1.4 0.3 0.1 Na2 ~ _ - 1.1 0.5 0.2 C/S ratio 1.9 3.1 1.8 0.07 o.g i.O
*Semiquantitative analysis; petrographic examination indicates dicalcium silicate i9 dominant phase.
As can be seen, the compositions range from ~hose (such as 8, 9 and 10~ in which a~l the aggrega~e is a stabil-ized lime aggrega~e, through the bulk of the compositions whlch contain stabilized lime aggregate together with peri-clase aggregate, up to compositlons such as 11 and 12 whichcontain dolomite as well as periclase and stabilized lime aggregate.
The compositions according to this invention were admixed in a V-Blender mixer for 5 minutes and were trans-10 fPrred ~o a batch gun wherein water was admixed wi~h ~he com-positions at the nozzle as they were gunned on~o a furnace wall. ~11 gunned well with smooth, surgeless 10w, and exhibi~ed a good water range, for ex~mple from 6 to 20%
water. Thsy build up well on ~he furnac~ wall and had low 15 rebound, ranging from about 6 to about 18%.
In addi~ion, Compositions 3, 4 and 6 have been commercially produced and used to repair the linings of electric arc urnaces, where they performed well ~nd enabled the operators to main~ain the linings indefinitely. In 2Q other words, ~hey gave as good service as prior art mixes containing raw materials costing 8 or more times the cost of ~he stabilized lime aggregates used in this invention.
Composi~ions 13, 14 and lS, made with stabilized lime aggregates outside ~he sc~pe of this inven~ion~ were 25 similarly admixed and gunned, but showed various deficiencies.
For exampleg Compositions 14 and 15 exhibited a distinct odor of hydrogen sulfide (H2S) when gunned; in addition~
the gunned samples mel~ed at 1455C and dripped off the ~est ~urnace wall. In other words~ Compositions 14 and 15 were 30 not sufficiently refrac~ory. COmpOSitiQn 13, while not show~
ing the hydrogen sulfide odor, did show a vitrified layer 2-1/2 inches (64 cm) deep when burned in at 1495C, whereas comparable Composition 4, when burned into the same tempera-ture 9 showed only 1 ;nch (2.5 cm) depth of vitrification.
35 This shows the much greater refractoriness o~ Composi~ion 4 compared to Composition 13, and indicates that the latter composition would be unsuitable for use in furnaces such as steel-producing furnaces.
2~
In summaryg i~ ;s the discovery of this invention tha~ it is possible to produce an efective gun mix from relatively low cost raw materials if the gun m~x includes a stabilized lime aggregate selected in accordance with the criteria of this invention, namely that it contain a~ least 75% total CaO ~ Fe203 ~ S102 ~ MgO, that the CaO:SiO2 weight ratio is at least 1.8 and that ît contain less than 7% free limeO While compositions con~aining as little as 5% stabilized lime aggregate are effective, best results are lO obtained with mixes containing at least 25% of such _ aggregate.
*Semiquantitative analysis; petrographic examination indicates dicalcium silicate i9 dominant phase.
As can be seen, the compositions range from ~hose (such as 8, 9 and 10~ in which a~l the aggrega~e is a stabil-ized lime aggrega~e, through the bulk of the compositions whlch contain stabilized lime aggregate together with peri-clase aggregate, up to compositlons such as 11 and 12 whichcontain dolomite as well as periclase and stabilized lime aggregate.
The compositions according to this invention were admixed in a V-Blender mixer for 5 minutes and were trans-10 fPrred ~o a batch gun wherein water was admixed wi~h ~he com-positions at the nozzle as they were gunned on~o a furnace wall. ~11 gunned well with smooth, surgeless 10w, and exhibi~ed a good water range, for ex~mple from 6 to 20%
water. Thsy build up well on ~he furnac~ wall and had low 15 rebound, ranging from about 6 to about 18%.
In addi~ion, Compositions 3, 4 and 6 have been commercially produced and used to repair the linings of electric arc urnaces, where they performed well ~nd enabled the operators to main~ain the linings indefinitely. In 2Q other words, ~hey gave as good service as prior art mixes containing raw materials costing 8 or more times the cost of ~he stabilized lime aggregates used in this invention.
Composi~ions 13, 14 and lS, made with stabilized lime aggregates outside ~he sc~pe of this inven~ion~ were 25 similarly admixed and gunned, but showed various deficiencies.
For exampleg Compositions 14 and 15 exhibited a distinct odor of hydrogen sulfide (H2S) when gunned; in addition~
the gunned samples mel~ed at 1455C and dripped off the ~est ~urnace wall. In other words~ Compositions 14 and 15 were 30 not sufficiently refrac~ory. COmpOSitiQn 13, while not show~
ing the hydrogen sulfide odor, did show a vitrified layer 2-1/2 inches (64 cm) deep when burned in at 1495C, whereas comparable Composition 4, when burned into the same tempera-ture 9 showed only 1 ;nch (2.5 cm) depth of vitrification.
35 This shows the much greater refractoriness o~ Composi~ion 4 compared to Composition 13, and indicates that the latter composition would be unsuitable for use in furnaces such as steel-producing furnaces.
2~
In summaryg i~ ;s the discovery of this invention tha~ it is possible to produce an efective gun mix from relatively low cost raw materials if the gun m~x includes a stabilized lime aggregate selected in accordance with the criteria of this invention, namely that it contain a~ least 75% total CaO ~ Fe203 ~ S102 ~ MgO, that the CaO:SiO2 weight ratio is at least 1.8 and that ît contain less than 7% free limeO While compositions con~aining as little as 5% stabilized lime aggregate are effective, best results are lO obtained with mixes containing at least 25% of such _ aggregate.
Claims (8)
1. A refractory composition suitable for gunning consisting essentially of from 5 to 95% of a stabilized lime aggregate, said aggregate containing at least 75%
total CaO + Fe2O3 + SiO2 + MgO, the remainder being other refractory oxides, the CaO:SiO2 weight ratio being at least 1.8, whereby dicalcium silicate is a major crystalline phase in the aggregate, said aggregate having less than 7%
free lime, from 1 to 10% of a basic inorganic bond, and from 0.05 to 5% plasticizer, the balance of the composition being basic refractory aggregate, all percentages being by weight based on the total weight of the composition.
total CaO + Fe2O3 + SiO2 + MgO, the remainder being other refractory oxides, the CaO:SiO2 weight ratio being at least 1.8, whereby dicalcium silicate is a major crystalline phase in the aggregate, said aggregate having less than 7%
free lime, from 1 to 10% of a basic inorganic bond, and from 0.05 to 5% plasticizer, the balance of the composition being basic refractory aggregate, all percentages being by weight based on the total weight of the composition.
2. Composition according to claim 1 containing at least 25% stabilized lime aggregate.
3. Composition according to claim 1 wherein the stabilized lime aggregate contains at least 20% by weight CaO.
4. Composition according to claim 3 containing at least 25% stabilized lime aggregate.
5. Composition according to claim 1 wherein the basic refractory aggregate is periclase containing at least 80% MgO.
6. Composition according to claim 2 wherein the basic refractory aggregate is periclase containing at least 80% MgO.
7. Composition according to claim 3 wherein the basic refractory aggregate is periclase containing at least 80% MgO.
8. Composition according to claim 4 wherein the basic refractory aggregate is periclase containing at least 80% MgO.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US512,073 | 1983-07-08 | ||
| US06/512,073 US4463100A (en) | 1983-07-08 | 1983-07-08 | Refractory gun mix |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1204792A true CA1204792A (en) | 1986-05-20 |
Family
ID=24037561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000434475A Expired CA1204792A (en) | 1983-07-08 | 1983-08-12 | Refractory gun mix |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4463100A (en) |
| EP (1) | EP0131391A3 (en) |
| JP (1) | JPS6036382A (en) |
| AU (1) | AU559877B2 (en) |
| CA (1) | CA1204792A (en) |
| NZ (1) | NZ208819A (en) |
| ZA (1) | ZA844501B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6168367A (en) * | 1984-09-12 | 1986-04-08 | 品川白煉瓦株式会社 | Basic refractory composition |
| US4843044A (en) * | 1988-03-01 | 1989-06-27 | Quigley Company, Inc. | Refractory composition |
| US5001092A (en) * | 1988-12-02 | 1991-03-19 | Quigley Company Inc. | Sodium sulfate containing refractory composition |
| US8747546B2 (en) * | 2007-08-17 | 2014-06-10 | Specialty Minerals (Michigan) Inc. | Calcium enriched refractory material by the addition of calcium carbonate |
| TW200925135A (en) * | 2007-08-17 | 2009-06-16 | Specialty Minerals Michigan | Calcium enriched refractory material by the addition of calcium carbonate |
| US20120028786A1 (en) * | 2010-07-30 | 2012-02-02 | Empire Technology Development Llc | Fabrication of cordierite article using waste steel slags |
| CN110818402B (en) * | 2019-08-19 | 2020-10-23 | 横店集团东磁股份有限公司 | Preparation method of superfine ferrite powder |
| CN116246876B (en) * | 2023-03-16 | 2024-01-19 | 天通控股股份有限公司 | High-permeability high-Bs flexible magnetic sheet and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US710916A (en) * | 1901-11-11 | 1902-10-07 | George Westinghouse | Lining for converters or furnaces. |
| FR796160A (en) * | 1934-10-17 | 1936-03-31 | Improvements to refractory materials | |
| FR837696A (en) * | 1938-05-07 | 1939-02-15 | Calcium silicate bonding process | |
| US2291917A (en) * | 1939-11-06 | 1942-08-04 | Canadian Refractories Ltd | Spalling-resistant refractory |
| FR987265A (en) * | 1949-05-24 | 1951-08-10 | Canadian Refractories Ltd | Method of consolidation of refractory materials |
| DE1088403B (en) * | 1957-02-08 | 1960-09-01 | Canadian Refractories Ltd | Refractory material |
| US3193402A (en) * | 1961-12-21 | 1965-07-06 | Basic Inc | Refractory composition for repairing furnaces |
| US3262793A (en) * | 1963-11-12 | 1966-07-26 | Kaiser Aluminium Chem Corp | Refractory |
| US3798043A (en) * | 1972-12-06 | 1974-03-19 | Airco Inc | High strength refractory concrete |
| FI63926C (en) * | 1978-04-18 | 1983-09-12 | Outokumpu Oy | FERROKROMSLAGG FOER AENDMAOL SOM KRAEVER ELDFASTHET OCH MEKANISK HAOLLFASTHET |
| SU933654A1 (en) * | 1979-03-28 | 1982-06-07 | Донецкий научно-исследовательский институт черной металлургии | Gunnite composition for convertor lining |
-
1983
- 1983-07-08 US US06/512,073 patent/US4463100A/en not_active Expired - Lifetime
- 1983-08-12 CA CA000434475A patent/CA1204792A/en not_active Expired
-
1984
- 1984-06-12 EP EP84303954A patent/EP0131391A3/en not_active Withdrawn
- 1984-06-14 ZA ZA844501A patent/ZA844501B/en unknown
- 1984-07-06 AU AU30368/84A patent/AU559877B2/en not_active Ceased
- 1984-07-06 JP JP59139190A patent/JPS6036382A/en active Pending
- 1984-07-06 NZ NZ208819A patent/NZ208819A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA844501B (en) | 1986-10-29 |
| US4463100A (en) | 1984-07-31 |
| AU3036884A (en) | 1985-01-10 |
| EP0131391A2 (en) | 1985-01-16 |
| NZ208819A (en) | 1986-12-05 |
| JPS6036382A (en) | 1985-02-25 |
| EP0131391A3 (en) | 1986-12-30 |
| AU559877B2 (en) | 1987-03-19 |
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